Preparation of titanium dioxide



Patented Feb. 1,1944 I I v umrao STATES PATENT orr'ica PREPARATION DIOXIDE i Irving E. Muskat, Akron, and Alphonse Pechukas, Barberton, Ohio, assignorsto Pittsburgh Plate Glass Company, Allegheny County, Pa., a corporation of Pennsylvania Application May 4, 1939, Serial No. 271,694

2 Claims. (Cl. 23-202) This invention relates to the preparation of tion of the furnace and spraying or showering metallic oxides such as titanium dioxide by drops of titanium tetrachloride through this atthermal decomposition of titanium tetrachloride mosphere into the oxidizing zone within the furin the presence of oxidizing gases. Prior to the nace. In any case, the accumulation of a reactpresent invention, numerous attempts have been 5 ing concentration of oxygen immediately adjamade to devise a process of thermally decomcent the tetrachloride inlet may be prevented. posing this compound. In general, the product In accordance with a further modification, it obtained in such cases, was found to be coarse, is found convenient to use the chlorine resulting crystalline, and unsuitable for use as a pigment. from the decomposition of the titanium tetra- In a prior application of Irving E. Muskat, Serial l0 chloride for the establishment of the inert at- No. 176,647, filed November 26, 1937, now U. S. mosphere. This may be done in suitable man- Patent No. 2,240,343, a process was described-for ner by constructing the apparatus so that chlopreventlng the formation of crystals. It was rine evolved during the reaction is swept back I noted in that application that crystal formation over the surface of the titanium tetrachloride could be prevented by preventing decomposition inlet. For example, we have been able to proof titanium tetrachloride adjacent hot surfaces. vide a suitable device wherein air or oxygen and This may be done by preventing contact of the titanium tetrachloride are introduced into the titanium tetrachloride with hot surfaces and/or reaction'zone in opposed directions and the chlo-- preventing accumulation of oxygen adjacent such rine produced is withdrawn along the exterior surfaces whereby decomposition is prevented or of thetitanium tetrachloride inlet. This phase substantially minimized. of the invention may be fully understood by In accordance with the present invention we reference to the accompanying drawing which is have provided novel methods for thermally dea diagrammatic sectional view of an apparacomposing titanium tetrachloride and for mini-, tus which may be used in accordance with this mizing crystal formation. We have found that. an invention; crystal formation may be substantially mini- In this embodiment we may use a vertical mized by maintaining an atmosphere of a suitcylindrical furnace I, which may be provided able gas such as chlorine which is capable of with areaction chamber 5, and a preheating preventing the oxidation of the tetrachloride chamber 2. The preheating chamber is provided adjacent the point at which it is introduced into with suitable heating elements 3, and if desired, the reaction chamber. The presence of a chlothe reaction chamber may also be heated in this rine atmosphere in this area not only minimanner with elements not shown. The furnace mizes the accumulation of oxygen adjacent the may be covered with suitable insulation i0, and inlet for titanium tetrachloride but also tends to is constructed to communicate with a separating rechlorinate any titanium dioxide which may chamber 6, in which titanium dioxide may be be inadvertently formed at this point. Thus, .removed from the reaction gases. The furnace the tendency for the growth of buds, or crystals of is also provided with titanium tetrachloride intitanium dioxide on the inlet nozzle is prevented. let I, which may be heated by heating element 8. In addition, when chlorine is used as the pro- In the operation of the device, air, oxygen or tective medium, there will be no dilution of the 40 other oxidizing gas is introduced in a downchlorine formed during the reaction as would wardly directed stream into the upper portion of be the case where inert gases are employed. the furnace at 4, and is preheated in preheater 2, Various methods of introducing the chlorine by means of heating element 3. At the same into the reaction chamber may be used. .Thus, time titanium tetrachloride, with or without a titanium tetrachloride vapor may be introduced suitable'diluent such as nitrogen, chlorine or through a nozzle or tube which is placed concencarbon dioxide, is introduced into tube 1, and is trically withina second larger tube or nozzle heated by element 8, as it passes upwardlyinto through which chlorine is allowed to flow. In the furnace. The tetrachloride is decomposed to such a case a stream of chlorine may flow conform titanium dioxide and chlorine when it continuously or intermittently past the tetrachlotacts the hot stream of oxygen. The chlorine ride inlet thus sweeping'the titanium tetra- 4 and suspended titanium dioxide are then withchlorlde away from the inlet and into the reacdrawn along the exposed portions of inlet tube 1,

tion zonewhere it is decomposed. In addition, and after removal of the solid titanium dioxide, the titanium tetrachloride may be introduced chlorine is withdrawn at outlet 9. The flow rates by establishing a chlorine atmosphere in a porto of oxygen'and titanium tetrachloride are adtetrachloride inlet. -regulated to introduce oxygen and titanium justedso that substantially all of the oxygen is reacted and no substantial quantity of gaseous oxygen remains in the chlorine gas which is withdrawn along the exterior of the titanium Ordinarily the process is tetrachloride in the stoichiometric amounts required for production of titanium dioxide. However, small excesses of the order of 5 to percent of either material are found to be unobjectionable.

If desired, the process may be conducted using a substantial excess of titanium tetrachloride. In such a case the atmosphere about the inlet may contain titanium tetrachloride but will not thermally'decompose at that point to an appreciable degree due to the substantial absence of oxygen.

It will be apparent that by proper regulation of the size of the chamber and of the rates of introduction of oxygen and titanium tetrachloride and of withdrawal of evolved chlorine it is possible to conduct the process in a manner such that oxygen and titanium tetrachloride do not accumulate in reacting concentrations adjacent the hot walls of the chamber. Conseqently, decomposition of the tetrachloride adjacent the hot surfaces with undesirable crystal formation is avoided. The prevention of the crystal formation may be facilitated by introducing the titanium tetrachloride at high speeds whereby it is removed from the inlet before decomposition can occur.- Crystal formation adjacent the wall of the decomposition chamber may be prevented by v maintainin a nonreactive body Of gas adjacent such walls. Thus, chlorine, nitrogen, titanium tetrachloride or mixtures of chlorine, nitrogen and/or titanium tetrachloride may be maintained about the walls by any convenient method. If desired, portions of the exhaust chlorine may be withdrawn adjacent the walls or a stream of inert gas may be caused to flow along the walls. Similarly, an inert gas may be maintained in a quiescent state adjacent the walls by use of a chamber of proper size and construction whereby oxygen is not introduced and does not accumulate near the walls.

ated for a period of 5% hours and a yield of 96 percent of pigmentary titanium dioxide was obtalned. vThe amount of crystals formed was negligible.

Example I per minute. The temperatur was maintained at l800 F. through the duration of the reaction. The product was very fine and possessed a good color. The amount of coarse crystals formed was below 0.5 percent of the total T102 formed.

In order to insure substantially complete absence of oxygen adjacent hot surfaces and thus prevent decomposition at these points, it is often desirable to maintain a quantity of carbon adjacent such surfaces. Thus, coatings of carbon may be applied to the exterior of the titanium tetrachloride nozzle and/ or or the walls of the furnace. Similarly all or a portion of the exposed walls and/or nozzle may be constructed of carbon or other agent capable of reacting with oxygen, such as nonvolatile halides, for example, magnesium or calcium chloride.

Although the present invention has been described with reference to the specific detail of certain embodiments thereof, it is not intended that such details shall be regarded as limitations upon the scope of the invention except insofar as included in the accompanying claims.

We claim:

1. In a method of preparing titanium dioxide 'by reacting titanium tetrachloride in vapor form with oxygen, the improvement which comprises introducing titanium tetrachloride vapors and a gas containing free oxygen into a reaction zone in substantially opposite directions and withdrawing the reaction products from the reaction zone in such direction and at such a. rate that the 4a evolved chlorine therein is carried by and sur- Whlle the temperature at which thermal decomposition of titanium tetrachloride is to be secured may be varied considerably, it is generally found that maximum yields of pigmentary materials may be secured at temperatures of 1500 to 2000 F. or above. Lower temperatures may be used but tend to result in lower yield of pigment. The titanium dioxide produced by this process is usually in the form of a fine powder or dust. The following examples are illustrative.

Eaiample I Using an apparatus having the general structure as shown in the accompanying drawing, air was introduced into a reaction zone having an internal diameter of 14 inches at the rate of 1301. per minute and titanium tetrachloride countercurrently introduced through a tube having an internal diameter of inch at a rate of 33.6 1. per minute. The temperature was maintained at 1800 F. throughout the reaction and the reaction products containing chlorine gas were withdrawn along the exterior of the titanium inlet tube and conducted to the settling chamher where suspended titanium dioxide was recovered. The process was continuously operrounds the point of introduction of titanium tetrachloride; the tetrachloride vapors and oxygen being introduced in such relative amounts and under such conditions of temperature and flow as to avoid any substantial concentration of free oxygen in the evolved chlorine at the point of introduction of titanium tetrachloride whereby formation of titanium dioxide adjacent thereto is prevented.

2. In a nlethod of preparing titanium dioxideby reacting titanium tetrachloride in vapor form with oxygen, the improvement which comprises introducing titanium tetrachloride vapors and oxygen into a reaction zone in substantially opposite directions and withdrawing the reaction products from the reaction zone in such direction and at such a rate that the evolved chlorine therein is carried by and surrounds the point of introduction of titanium tetrachloride; the tetrachloride vapors and oxygen being introduced in such relative amounts and under such conditions of temperature and flow as to avoid any substantial concentration of free oxygen in the evolved chlorine at the point of introduction of titanium tetrachloride whereby formation of titanium dioxide adjacent thereto is prevented.

IRVING E. MUSKAT. ALPHONSE PECHUKAS. 

